Organic catalyst with enhanced solubility

ABSTRACT

This invention relates to organic catalysts comprising iminium or oxaziridinium moieties, cleaning compositions comprising such catalysts; and processes for making and suing such catalysts and cleaning products.

CROSS-REFERENCES TO RELATED APPLICATIONS

[0001] This application claims priority under 35 U.S.C. § 119(e) to U.S.Provisional Application Serial No. 60/386,692 filed Jun. 6, 2002 andU.S. Provisional Application Serial No. 60/426,549 filed Nov. 15, 2002.

FIELD OF INVENTION

[0002] This invention relates to organic catalysts and cleaningcompositions comprising such catalysts; and processes for making andusing such catalysts and cleaning products.

BACKGROUND OF THE INVENTION

[0003] Oxygen bleaching agents, for example hydrogen peroxide, aretypically used to facilitate the removal of stains and soils fromclothing and various surfaces. Unfortunately such agents are extremelytemperature rate dependent. As a result, when such agents are employedin colder solutions, the bleaching action of such solutions is markedlydecreased.

[0004] In an effort to resolve the aforementioned performance problem,the industry developed a class of materials known as “bleachactivators”. However, as such materials rapidly lose their effectivenessat solution temperatures of less than 40° C., new organic catalysts suchas 3,4-dihydro-2-[2-(sulfooxy)decyl]isoquinolimium, inner salt weredeveloped. In general, while such solubility is limited. As most laundryand cleaning compositions are formulated in, or intended to be used withwater, formulating cleaning products with such catalysts can beproblematic.

[0005] Accordingly, there is a need for an inexpensive organic catalystthat can provide the combined benefits of formulation flexibility, andlow water temperature bleaching performance.

SUMMARY OF THE INVENTION

[0006] The present invention relates to organic catalysts havingenhanced solubility. The present invention also relates to cleaningcompositions comprising said organic catalysts, and processes for makingand using the aforementioned organic catalysts and cleaningcompositions.

DETAILED DESCRIPTION OF THE INVENTION

[0007] Definitions

[0008] As used herein, the term “cleaning composition” includes, unlessotherwise indicated, granular or powder-form all-purpose or “heavy-duty”washing agents, especially laundry detergents; liquid, gel or paste-formall-purpose washing agents, especially the so-called heavy-duty liquidtypes; liquid fine-fabric detergents; hand dishwashing agents or lightduty dishwashing agents, especially those of the high-foaming type;machine dishwashing agents, including the various tablet, granular,liquid and rinse-aid types for household and institutional use; liquidcleaning and disinfecting agents, including antibacterial hand-washtypes, laundry bars, mouthwashes, denture cleaners, car or carpetshampoos, bathroom cleaners; hair shampoos and hair-rinses; shower gelsand foam baths and metal cleaners; as well as cleaning auxiliaries suchas bleach additives and “stain-stick” or pre-treat types.

[0009] As used herein, the phrase “is independently selected from thegroup consisting of . . . .” means that moieties or elements that areselected from the referenced Markush group can be the same, can bedifferent or any mixture of elements as indicated in the followingexample:

[0010] A molecule having 3 R groups wherein each R group isindependently selected from the group consisting of A, B and C.

[0011] Here the three R groups may be: AAA, BBB, CCC, AAB, AAC, BBA,BBC, CCA, CCB, ABC.

[0012] As used herein, “substituted” means that the organic compositionor radical to which the term is applied is:

[0013] (a) made unsaturated by the elimination of elements or radical;or

[0014] (b) at least one hydrogen in the compound or radical is replacedwith a moiety containing one or more (i) carbon, (ii) oxygen, (iii)sulfur, (iv) nitrogen or (v) halogen atoms; or

[0015] (c) both (a) and (b).

[0016] Moieties that may replace hydrogen as described in (b)immediately above, which contain only carbon and hydrogen atoms are allhydrocarbon moieties including, but not limited to, alkyl, alkenyl,alkynyl, alkyldienyl, cycloalkyl, phenyl, alkyl phenyl, naphthyl,anthryl, phenanthryl, fluoryl, steroid groups, and combinations of thesegroups with each other and with polyvalent hydrocarbon groups such asalkylene, alkylidene and alkylidyne groups. Specific non-limitingexamples of such groups are:

—CH₃, —CHCH₃CH₃, —(CH₂)SCH₃, —CH₂—C≡CH, —CH═CH—CH═CH₂,

[0017]

 —φCH₃, —φCH₂φ, —φ, and —φ—φ.

[0018] Moieties containing oxygen atoms that may replace hydrogen asdescribed in (b) immediately above include hydroxy, acyl or keto, ether,epoxy, carboxy, and ester containing groups. Specific non-limitingexamples of such oxygen containing groups are:

—CH₂OH, —CCH₃CH₃OH, —CH₂COOH, —C(O)—(CH₂)₈CH₃, —OCH₂CH₃, ═O, —OH,

—CH₂—O—CH₂CH₃, —CH₂—O—(CH₂)₂—OH, —CH₂CH₂COOH, —φOH, —φOCH₂CH₃,

—φCH₂OH,

[0019]

[0020] Moieties containing sulfur atoms that may replace hydrogen asdescribed in (b) immediately above include the sulfur-containing acidsand acid ester groups, thioether groups, mercapto groups and thioketogroups. Specific non-limiting examples of such sulfur containing groupsare: —SCH₂CH₃, —CH₂S(CH₂)₄CH₃, —SO₃CH₂CH₃, SO₂CH₂CH₃, —CH₂COSH, —SH,—CH₂SCO, —CH₂C(S)CH₂CH₃, —SO₃H, —O(CH₂)₂C(S)CH₃, ═S, and

[0021] Moieties containing nitrogen atoms that may replace hydrogen asdescribed in (b) immediately above include amino groups, the nitrogroup, azo groups, ammonium groups, amide groups, azido groups,isocyanate groups, cyano groups and nitrile groups. Specificnon-limiting examples of such nitrogen containing groups are: —NHCH₃,—NH₂, —NH₃ ⁺, —CH₂CONH₂, —CH₂CON₃, —CH₂CH₂CH═NOH, —CAN, —CH(CH₃)CH₂NCO,—CH₂NCO, —Nφ, —φN═NφOH, and ≡N.

[0022] Moieties containing halogen atoms that may replace hydrogen asdescribed in (b) immediately above include chloro, bromo, fluoro, iodogroups and any of the moieties previously described where a hydrogen ora pendant alkyl group is substituted by a halo group to form a stablesubstituted moiety. Specific non-limiting examples of such halogencontaining groups are: —(CH₂)₃COCl, —φOF₅, —Cl, —CF₃, and —CH₂φBr.

[0023] It is understood that any of the above moieties that may replacehydrogen as described in (b) can be substituted into each other ineither a monovalent substitution or by loss of hydrogen in a polyvalentsubstitution to form another monovalent moiety that can replace hydrogenin the organic compound or radical.

[0024] As used herein “φ” represents a phenyl ring.

[0025] All documents cited are, in relevant part, incorporated herein byreference; the citation of any document is not to be construed as anadmission that it is prior art with respect to the present invention.

[0026] Organic Catalyst

[0027] In one aspect of Applicants' invention, Applicants' catalyst hasFormula 1 below:

[0028] wherein: R₁ is a aryl or heteroaryl group that can be substitutedor unsubstituted;

[0029] R₂ is a substituted or unsubstituted alkyl;

[0030] R₁ and R₂ when taken together with the iminium form a ring

[0031] R₃ is a C₁ to C₂₀ substituted alkyl;

[0032] R₄ is the moiety Q_(t)—A

[0033] wherein: Q is a branched or unbranched alkylene

[0034] t=0 or 1 and

[0035] A is an anionic group selected from the group consisting of OSO₃⁻, SO₃ ⁻, CO₂ ⁻, OCO₂ ⁻, OPO₃ ²⁻, OPO₃H⁻ and OPO₂ ⁻;

[0036] R₅ is the moiety —CR₁₁R₁₂—X—G_(b)—X_(c)—[(CR₉R₁₀)_(y)—O]_(k)—R₈

[0037] wherein: each X is independently selected from the groupconsisting of O, S, N—H, or N—R₈; and

[0038] each R₈ is independently selected from the group consisting ofalkyl, aryl and heteroaryl, said R₈ moieties being substituted orunsubstituted, and whether substituted or unsubsituted said R₈ moietieshaving less than 21 carbons;

[0039] each G is independently selected from the group consisting of CO,SO₂, SO, PO and PO₂;

[0040] R₉ and R₁₀ are independently selected from the group consistingof H and C₁-C₄ alkyl; and

[0041] R₁₁ and R₁₂ are independently selected from the group consistingof H and alkyl, or when taken together may join to form a carbonyl; and

[0042] b=0 or 1;

[0043] c can=0 or 1, but c must=0 if b=0;

[0044] y is an integer from 1 to 6;

[0045] k is an integer from 0 to 20; and

[0046] R₆ is H, or an alkyl, aryl or heteroaryl moiety; said moietiesbeing substituted or unsubstituted.

[0047] In another aspect of Applicants' invention, Applicants' catalysthas the Formula 1 above

[0048] wherein: R₁ is a aryl or heteroaryl group that can be substitutedor unsubstituted;

[0049] R₂ is a substituted or unsubstituted alkyl;

[0050] R₁ and R₂ when taken together with the iminium form a ring;

[0051] R₃ is a C₁ to C₁₂ substituted alkyl;

[0052] R₄ is the moiety Q_(t)—A

[0053] wherein: Q is a C₁ to C₃ alkyl;

[0054] t=0 or 1 and

[0055] A is an anionic group selected from the group consisting of OSO₃⁻, SO₃ ⁻, CO₂ ⁻, and OCO₂ ⁻;

[0056] R₅ is the moiety —CR₁₁R₁₂—X—G_(b)—X_(c)—R₈

[0057] wherein: each X is independently selected from the groupconsisting of O, S, N—H, or N—R₈; and

[0058] each R₈ is independently selected from the group consisting ofalkyl, aryl and heteroaryl, said R₈ moieties being substituted orunsubstituted, and whether substituted or unsubsituted said R₈ moietieshaving less than 21 carbons;

[0059] each G is independently selected from the group consisting of CO,SO₂, SO, PO and PO₂;

[0060] R₁₁, and R₁₂ are independently selected from the group consistingof H and alkyl;

[0061] b=0 or 1;

[0062] c can=0 or 1, but c must=0 if b=1; and

[0063] R₆ is H, or an alkyl, aryl or heteroaryl moiety; said moietiesbeing substituted or unsubstituted.

[0064] In another aspect of Applicants' invention, Applicants' catalysthas Formula 1 above:

[0065] wherein: R₁ is a aryl or heteroaryl group that can be substitutedor unsubstituted;

[0066] R₂ is a substituted or unsubstituted alkyl;

[0067] R₁ and R₂ when taken together with the iminium form a sixmembered ring;

[0068] R₃ is a substituted C₂ alkyl;

[0069] R₄ is OSO₃ ⁻;

[0070] R₅ is the moiety —CH₂—O—R₈ wherein R₈ is independently selectedfrom the group consisting of alkyl, aryl and heteroaryl, said R₈ moietybeing substituted or unsubstituted, and whether substituted orunsubsituted said R₈ moiety having less than 21 carbons; and

[0071] R₆ is H, or an alkyl, aryl or heteroaryl moiety; said moietiesbeing substituted or unsubstituted.

[0072] In another aspect of Applicants' invention, Applicants' catalysthas Formula 2 below:

[0073] wherein: R₁ is a aryl or heteroaryl group that can be substitutedor unsubstituted;

[0074] R₂ is a substituted or unsubstituted alkyl;

[0075] R₁ and R₂ when taken together with the carbon and the nitrogen ofthe oxaziridinium form a ring;

[0076] R₃ is a C₁ to C₂₀ substituted alkyl;

[0077] R₄ is the moiety Q_(t)—A

[0078] wherein: Q is a branched or unbranched alkylene

[0079] t=0 or 1 and

[0080] A is an anionic group selected from the group consisting of OSO₃⁻, SO₃ ⁻, CO₂ ⁻, OCO₂ ⁻, OPO₃ ²⁻, OPO₃H⁻ and OPO₂ ⁻;

[0081] R₅ is the moiety —CR₁₁R₁₂—X—G_(b)—X_(c)—[(CR₉R₁₀)_(y)—O]_(k)—R₈

[0082] wherein: each X is independently selected from the groupconsisting of O, S, N—H, or N—R₈; and

[0083] each R₈ is independently selected from the group consisting ofalkyl, aryl and heteroaryl, said R₈ moieties being substituted orunsubstituted, and whether substituted or unsubsituted said R₈ moietieshaving less than 21 carbons;

[0084] each G is independently selected from the group consisting of CO,SO₂, SO, PO and PO₂;

[0085] R₉ and R₁₀ are independently selected from the group consistingof H and C₁-C₄ alkyl; and

[0086] R₁₁ and R₁₂ are independently selected from the group consistingof H and alkyl, or when taken together may form a carbonyl;

[0087] b=0 or 1;

[0088] c can=0 or 1, but c must=0 if b=0;

[0089] y is an integer from 1 to 6;

[0090] k is an integer from 0 to 20; and

[0091] R₆ is H, or an alkyl, aryl or heteroaryl moiety; said moietiesbeing substituted or unsubstituted.

[0092] In another aspect of Applicants' invention, Applicants' catalysthas the Formula 2 above:

[0093] wherein: R₁ is a aryl or heteroaryl group that can be substitutedor unsubstituted;

[0094] R₂ is a substituted or unsubstituted alkyl;

[0095] R₁ and R₂ when taken together with the carbon and the nitrogen ofthe oxaziridinium form a ring;

[0096] R₃ is a C₁ to C₁₂ substituted alkyl;

[0097] R₄ is the moiety Q_(t)—A

[0098] wherein: Q is a C₁ to C₃ alkyl;

[0099] t=0 or 1 and

[0100] A is an anionic group selected from the group consisting of OSO₃⁻, SO₃ ⁻, CO₂ ⁻, and OCO₂ ⁻;

[0101] R₅ is the moiety —CR₁₁R₁₂—X—G_(b)—X_(c)—R₈

[0102] wherein: each X is independently selected from the groupconsisting of O, S, N—H, or N—R₈; and

[0103] each R₈ is independently selected from the group consisting ofalkyl, aryl and heteroaryl, said R8 moieties being substituted orunsubstituted, and whether substituted or unsubsituted said R₈ moietieshaving less than 21 carbons;

[0104] each G is independently selected from the group consisting of CO,SO₂, SO, PO and PO₂;

[0105] R₁₁ and R₁₂ are independently selected from the group consistingof H and alkyl;

[0106] b=0 or 1;

[0107] c can 0 or 1, but c must=0 if b=1; and

[0108] R₆ is H, or an alkyl, aryl or heteroaryl moiety; said moietiesbeing substituted or unsubstituted.

[0109] In another aspect of Applicants' invention, Applicants' catalysthas Formula 2 above:

[0110] wherein: R₁ is a aryl or heteroaryl group that can be substitutedor unsubstituted;

[0111] R₂ is a substituted or unsubstituted alkyl;

[0112] R₁ and R₂ when taken together with the carbon and the nitrogen ofthe oxaziridinium form a six member ring;

[0113] R₃ is a substituted C₂ alkyl;

[0114] R₄ is OSO₃ ⁻;

[0115] R₅ is the moiety —CH₂—O—R₈ wherein R₈ is independently selectedfrom the group consisting of alkyl, aryl and heteroaryl, said R₈ moietybeing substituted or unsubstituted, and whether substituted orunsubsituted said R₈ moiety having less than 21 carbons; and

[0116] R₆ is H, or an alkyl, aryl or heteroaryl moiety; said moietiesbeing substituted or unsubstituted.

[0117] Applicants have found that judicious selection of the R₅ moietyfor the organic catalyst embodiments of the present invention providesthe requisite enhanced solubility necessary to obtain the combinedbenefits of formulation flexibility, and low water temperature bleachingperformance. While not being bound by theory, Applicants believe this isdue to the dipole-enhancing and, optionally, crystallinity-inhibitingproperties of said R₅ moieties.

[0118] Processes of Making Organic Catalysts

[0119] Suitable routes for preparing Applicants' organic catalystsinclude, but are not limited to, the synthetic routes detailed below:

[0120] Alcohol 1 may be converted to halohydrin 2 via Lewis acidcatalyzed addition to epihalohydrin, followed by (a) base induced ringclosure to epoxide 3 and subsequent ring opening with HX, or (b) halogenexchange reaction. Halohydrin 2 may be converted to product 5 by (1)alkylating dihydroisoquinoline 9 and then sulfating (2 to 6 to 5), or(2) sulfating and then alkylating 9 (2 to 8 to 5). Alternatively, theproduct may be obtained from epoxide 3 via (1) conversion to cyclicsulfate 4 and reaction with dihydroisoquinoline 9, or (2) Lewis acidcatalyzed addition to 9 to form oxazolidine 7 which is opened underacidic conditions to 6 and subsequently sulfated. While the syntheticpathways detailed above employ specifically substituted reagents, aswill be appreciated by one skilled in the art, reagents with differentsubstituents may be employed if other products are desired.

[0121] Raw materials required for the aforementioned syntheses aregenerally commercial available. For example, glycidal ethers such as(2-ethylhexyloxy)oxiran-2-ylmethane can be acquired through the RaschigCorporation, 129 South Scoville Avenue, Oak Park Ill., 60302, U.S.A,under the product name EHGE. 3,4-Dihydroisoquinoline can be prepared bythe Bischler-Napieralski reaction, as described by Whaley et al (W.Whaley et al, Organic reactions (1951), VI 74-150). Halohydrins, such as1-Bromo-3-(2-ethyl-hexyloxy)-propan-2-ol and cyclic sulfates such as4-[(2-ethylhexyloxymethyl]-1,3,2-dioxathiolane-2,2-dione can be preparedby the detailed procedures described in Applicants Examples.

[0122] The synthesis paths that Applicants' developed allow commercialquantities of cyclic sulfate to be produced using falling film reactorswherein cyclic sulfate is produced by the process of: 1.) introducingthe appropriate glycidal ether into a dry stream of SO₃ gas, 2.)contacting said reagents within the falling film reactor, 3.) thenoptionally holding the resulting reaction mixture at a sufficienttemperature for a sufficient time to achieve the desired conversion, and4.) optionally isolating the resulting cyclic sulfate. As appreciated bythe skilled artisan, reaction conditions vary depending on equipmenttype. However, when in possession of the teachings contained herein,such conditions are easily determined.

[0123] Commercial quantities of Applicants' catalyst can be producedusing a variety of reaction vessels and processes including batch,semi-batch and continuous processes. Non-limiting procedures forproducing Applicants catalyst include contacting glycidal ether with anSO₃ complex, either neat or with an appropriate aprotic solvent for lessthan about 60 minutes, at a temperature of from about 75° C. to about130° C., and a pressure of about 1 atmosphere to form the desired cyclicsulfate. Final conversion to the desired organic catalyst is achieved bycontacting the cyclic sulfate with a 3,4-dihydroisoquinoline for lessthan about 24 hours, at a temperature of from about 20° C. to about 50°C., and a pressure of about 1 atmosphere.

[0124] In addition to the procedure described above, Applicants'catalyst can be produced by first producing a halohydrin, such as1-bromohydrin, by contacting a glycidal ether with hydrobromic acid forless than about 10 minutes, at a temperature of from about 0° C. toabout 40° C., and a pressure of about 1 atmosphere, and then isolatingthe 1-bromohydrin through conventional means that include but are notlimited to extraction and distillation. Next the 1-bromohydrin isreacted with a 3,4-dihydroisoquinoline for about 48 hours, at atemperature of about 40° C. and a pressure of about 1 atmosphere to formalcohol salt which is subsequently sulfated in the same reaction vesselvia a sulfating agent such as SO₃, an SO₃ complex, HSO₃Cl or mixturethereof to generate the desired product.

[0125] The oxaziridinium ring containing version of Applicants' catalystmay be produced by contacting an iminium ring containing version ofApplicants' catalysts with an oxygen transfer agent such as aperoxycarboxylic acid. Such species can be formed in situ and usedwithout purification.

[0126] Cleaning Compositions and Cleaning Composition AdditivesComprising Applicants' Organic Catalysts

[0127] The cleaning composition of the present invention may beadvantageously employed for example, in laundry applications, hardsurface cleaning, automatic dishwashing applications, as well ascosmetic applications such as dentures, teeth, hair and skin. However,due to the unique advantages of both increased effectiveness in lowertemperature solutions and the superior color-safety profile, the organiccatalysts of the present invention are ideally suited for laundryapplications such as the bleaching of fabrics through the use of bleachcontaining detergents or laundry bleach additives. Furthermore, theorganic catalysts of the present invention may be employed in bothgranular and liquid compositions.

[0128] The organic catalysts of the present invention may also beemployed in a cleaning additive product. A cleaning additive productincluding the organic catalysts of the present invention is ideallysuited for inclusion in a wash process when additional bleachingeffectiveness is desired. Such instances may include, but are notlimited to, low temperature solution cleaning application. The additiveproduct may be, in its simplest form, Applicants' organic catalyst.Preferably, the additive could be packaged in dosage form for additionto a cleaning process where a source of peroxygen is employed andincreased bleaching effectiveness is desired. Such single dosage formmay comprise a pill, tablet, gelcap or other single dosage unit such aspre-measured powders or liquids. A filler or carrier material may beincluded to increase the volume of such composition. Suitable filler orcarrier materials include, but are not limited to, various salts ofsulfate, carbonate and silicate as well as talc, clay and the like.Filler or carrier materials for liquid compositions may be water or lowmolecular weight primary and secondary alcohols including polyols anddiols. Examples of such alcohols include, but are not limited to,methanol, ethanol, propanol and isopropanol. The compositions maycontain from about 5% to about 90% of such materials. Acidic fillers canbe used to reduce pH. Alternatively, the cleaning additive may includeactivated peroxygen source defined below or the adjunct ingredients asfully defined below.

[0129] Applicants' cleaning compositions and cleaning additives requirea catalytically effective amount of Applicants' organic catalyst. Therequired level of such catalyst may be achieved by the addition of oneor more species of Applicants' organic catalyst. As a practical matter,and not by way of limitation, the compositions and cleaning processesherein can be adjusted to provide on the order of at least 0.001 ppm ofApplicants' organic catalyst in the washing medium, and will preferablyprovide from about 0.001 ppm to about 500 ppm, more preferably fromabout 0.005 ppm to about 150 ppm, and most preferably from about 0.05ppm to about 50 ppm, of the organic catalyst in the wash liquor. Inorder to obtain such levels in the wash liquor, typical compositionsherein will comprise from about 0.0002% to about 5%, more preferablyfrom about 0.001% to about 1.5%, of organic catalyst, by weight of thecleaning compositions.

[0130] When the Applicants' organic catalyst is employed in a granularcomposition, it may be desirable for the Applicants' organic catalyst tobe in the form of an encapsulated particle to protect the Applicants'organic catalyst from moisture and/or other components of the granularcomposition during storage. In addition, encapsulation is also a meansof controlling the availability of the Applicants' organic catalystduring the cleaning process and may enhance the bleaching performance ofthe Applicants' organic catalyst. In this regard, the Applicants'organic catalyst can be encapsulated with any encapsulating materialknown in the art.

[0131] The encapsulating material typically encapsulates at least part,preferably all, of the Applicants' organic catalyst. Typically, theencapsulating material is water-soluble and/or water-dispersible. Theencapsulating material may have a glass transition temperature (Tg) of0° C. or higher. Glass transition temperature is described in moredetail in WO 97/11151, especially from page 6, line 25 to page 7, line2. As such, WO 97/11151 is incorporated herein by reference.

[0132] The encapsulating material is preferably selected from the groupconsisting of carbohydrates, natural or synthetic gums, chitin andchitosan, cellulose and cellulose derivatives, silicates, phosphates,borates, polyvinyl alcohol, polyethylene glycol, paraffin waxes andcombinations thereof. Preferably the encapsulating material is acarbohydrate, typically selected from the group consisting ofmonosaccharides, oligosaccharides, polysaccharides, and combinationsthereof. Most preferably, the encapsulating material is a starch.Preferred starches are described in EP 0 922 499; U.S. Pat. No.4,977,252; U.S. Pat. No. 5,354,559 and U.S. Pat. No. 5,935,826.

[0133] The encapsulating material may be a microsphere made from plasticsuch as thermoplastics, acrylonitrile, methacrylonitrile,polyacrylonitrile, polymethacrylonitrile and mixtures thereof;commercially available microspheres that can be used are those suppliedby Expancel of Stockviksverken, Sweden under the trademark Expancel®,and those supplied by PQ Corp. of Valley Forge, Pa. U.S.A. under thetradename PM 6545, PM 6550, PM 7220, PM 7228, Extendospheres®, Luxsil®,Q-cel® and Sphericel®.

[0134] In addition to Applicants' organic catalysts, cleaningcompositions must comprise an activated peroxygen source. Suitableratios of moles of Applicants' organic catalyst to moles of activatedperoxygen source include but are not limited to from about 1:1 to about1:1000. Suitable activated peroxygen sources include, but are notlimited to, preformed peracids, a hydrogen peroxide source incombination with a bleach activator, or a mixture thereof. Suitablepreformed peracids include, but are not limited to, compounds selectedfrom the group consisting of percarboxylic acids and salts, percarbonicacids and salts, perimidic acids and salts, peroxymonosulfuric acids andsalts, and mixtures thereof. Suitable sources of hydrogen peroxideinclude, but are not limited to, compounds selected from the groupconsisting of perborate compounds, percarbonate compounds, perphosphatecompounds and mixtures thereof.

[0135] Suitable bleach activators include, but are not limited to,tetraacetyl ethylene diamine (TAED), benzoylcaprolactam (BzCL),4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam,benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS),phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C₁₀-OBS),benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (C₈-OBS),perhydrolyzable esters, perhydrolyzable imides and mixtures thereof

[0136] When present, hydrogen peroxide sources will typically be atlevels of from about 1%, preferably from about 5% to about 30%,preferably to about 20% by weight of the composition. If present,peracids or bleach activators will typically comprise from about 0.1%,preferably from about 0.5% to about 60%, more preferably from about 0.5%to about 40% by weight of the bleaching composition.

[0137] In addition to the disclosure above, suitable types and levels ofactivated peroxygen sources are found in U.S. Pat. Nos. 5,576,282,6,306,812 B1 and 6,326,348 B1 that are incorporated by reference.

[0138] The cleaning compositions herein will preferably be formulatedsuch that, during use in aqueous cleaning operations, the wash waterwill have a pH of between about 6.5 and about 11, preferably betweenabout 7.5 and 10.5. Liquid dishwashing product formulations preferablyhave a pH between about 6.8 and about 9.0. Laundry products aretypically at pH 9-11. Techniques for controlling pH at recommended usagelevels include the use of buffers, alkalis, acids, etc., and are wellknown to those skilled in the art.

[0139] Adjunct Materials

[0140] While not essential for the purposes of the present invention,the non-limiting list of adjuncts illustrated hereinafter are suitablefor use in the instant cleaning compositions and may be desirablyincorporated in preferred embodiments of the invention, for example toassist or enhance cleaning performance, for treatment of the substrateto be cleaned, or to modify the aesthetics of the cleaning compositionas is the case with perfumes, colorants, dyes or the like. The precisenature of these additional components, and levels of incorporationthereof, will depend on the physical form of the composition and thenature of the cleaning operation for which it is to be used. Suitableadjunct materials include, but are not limited to, surfactants,builders, chelating agents, dye transfer inhibiting agents, dispersants,enzymes, and enzyme stabilizers, catalytic metal complexes, polymericdispersing agents, clay soil removal/anti-redeposition agents,brighteners, suds suppressors, dyes, perfumes, structure elasticizingagents, fabric softeners, carriers, hydrotropes, processing aids and/orpigments. In addition to the disclosure below, suitable examples of suchother adjuncts and levels of use are found in U.S. Pat. Nos. 5,576,282,6,306,812 B1 and 6,326,348 B1 that are incorporated by reference.

[0141] Surfactants—Preferably, the cleaning compositions according tothe present invention comprise a surfactant or surfactant system whereinthe surfactant can be selected from nonionic and/or anionic and/orcationic surfactants and/or ampholytic and/or zwitterionic and/orserni-polar nonionic surfactants.

[0142] The surfactant is typically present at a level of from about0.1%, preferably about 1%, more preferably about 5% by weight of thecleaning compositions to about 99.9%, preferably about 80%, morepreferably about 35%, most preferably about 30% by weight of thecleaning compositions.

[0143] Builders—The cleaning compositions of the present inventionpreferably comprise one or more detergent builders or builder systems.When present, the compositions will typically comprise at least about 1%builder, preferably from about 5%, more preferably from about 10% toabout 80%, preferably to about 50%, more preferably to about 30% byweight, of detergent builder.

[0144] Builders include, but are not limited to, the alkali metal,ammonium and alkanolammonium salts of polyphosphates, alkali metalsilicates, alkaline earth and alkali metal carbonates, aluminosilicatebuilders polycarboxylate compounds. ether hydroxypolycarboxylates,copolymers of maleic anhydride with ethylene or vinyl methyl ether,1,3,5-trihydroxy benzene-2,4,6-trisulphonic acid, andcarboxymethyloxysuccinic acid, the various alkali metal, ammonium andsubstituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylatessuch as mellitic acid, succinic acid, oxydisuccinic acid, polymaleicacid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid,and soluble salts thereof.

[0145] Chelating Agents—The cleaning compositions herein may alsooptionally contain one or more copper, iron and/or manganese chelatingagents.

[0146] If utilized, these chelating agents will generally comprise fromabout 0.1% by weight of the cleaning compositions herein to about 15%,more preferably 3.0% by weight of the cleaning compositions herein.

[0147] Dye Transfer Inhibiting Agents—The cleaning compositions of thepresent invention may also include one or more dye transfer inhibitingagents. Suitable polymeric dye transfer inhibiting agents include, butare not limited to, polyvinylpyrrolidone polymers, polyamine N-oxidepolymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.

[0148] When present in the cleaning compositions herein, the dyetransfer inhibiting agents are present at levels from about 0.0001%,more preferably about 0.01%, most preferably about 0.05% by weight ofthe cleaning compositions to about 10%, more preferably about 2%, mostpreferably about 1% by weight of the cleaning compositions.

[0149] Dispersants—The cleaning compositions of the present inventioncan also contain dispersants. Suitable water-soluble organic materialsare the homo- or co-polymeric acids or their salts, in which thepolycarboxylic acid comprises at least two carboxyl radicals separatedfrom each other by not more than two carbon atoms.

[0150] Enzymes—The cleaning compositions can comprise one or moredetergent enzymes which provide cleaning performance and/or fabric carebenefits. Examples of suitable enzymes include, but are not limited to,hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases,phospholipases, esterases, cutinases, pectinases, keratanases,reductases, oxidases, phenoloxidases, lipoxygenases, ligninases,pullulanases, tannases, pentosanases, malanases, β-glucanases,arabinosidases, hyaluronidase, chondroitinase, laccase, and knownamylases, or mixtures thereof. A preferred combination is a cleaningcomposition having a cocktail of conventional applicable enzymes likeprotease, lipase, cutinase and/or cellulase in conjunction with amylase.

[0151] Enzyme Stabilizers—Enzymes for use in detergents can bestabilized by various techniques. The enzymes employed herein can bestabilized by the presence of water-soluble sources of calcium and/ormagnesium ions in the finished compositions that provide such ions tothe enzymes.

[0152] Catalytic Metal Complexes—Applicants' cleaning compositions mayinclude catalytic metal complexes. One type of metal-containing bleachcatalyst is a catalyst system comprising a transition metal cation ofdefined bleach catalytic activity, such as copper, iron, titanium,ruthenium, tungsten, molybdenum, or manganese cations, an auxiliarymetal cation having little or no bleach catalytic activity, such as zincor aluminum cations, and a sequestrate having defined stabilityconstants for the catalytic and auxiliary metal cations, particularlyethylenediarninetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Suchcatalysts are disclosed in U.S. Pat. No. 4,430,243 Bragg, issued Feb. 2,1982.

[0153] If desired, the compositions herein can be catalyzed by means ofa manganese compound. Such compounds and levels of use are well known inthe art and include, for example, the manganese-based catalystsdisclosed in U.S. Pat. No. 5,576,282 Miracle et al. Preferred examplesof these catalysts include Mn^(IV)₂(u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(PF₆)₂, Mn^(III)₂(u-O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₂,Mn^(IV) ₄(u-O)₆(1,4,7-triazacyclononane)₄(ClO₄)₄, Mn^(III)Mn^(IV)₄(u-O)₁(u-OAc)₂-(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₃,Mn^(IV)(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH₃)₃(PF₆), andmixtures thereof.

[0154] Cobalt bleach catalysts useful herein are known, and aredescribed, for example, in U.S. Pat. No. 5,597,936 Perkins et al.,issued Jan. 28, 1997; U.S. Pat. No. 5,595,967 Miracle et al., Jan. 21,1997. The most preferred cobalt catalyst useful herein are cobaltpentaamine acetate salts having the formula [Co(NH₃)₅OAc] T_(y), wherein“OAc” represents an acetate moiety and “T_(y)” is an anion, andespecially cobalt pentaamine acetate chloride, [Co(NH₃)₅OAc]Cl₂; as wellas [Co(NH₃)₅OAc](OAc)₂; [Co(NH₃)₅OAc](PF₆)₂; [Co(NH₃)₅OAc](SO₄);[Co-(NH₃)₅OAc](BF₄)₂; and [Co(NH₃)₅OAc](NO₃)₂ (herein “PAC”). Suchcobalt catalyst readily prepared by known procedures, such as taught forexample in U.S. Pat. No. 5,597,936, and U.S. Pat. No. 5,595,967.

[0155] Compositions herein may also suitably include a transition metalcomplex of a macropolycyclic rigid ligand—abreviated as “MRL”. As apractical matter, and not by way of limitation, the compositions andcleaning processes herein can be adjusted to provide on the order of atleast one part per hundred million of the active MRL species in theaqueous washing medium, and will preferably provide from about 0.005 ppmto about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm,and most preferably from about 0.1 ppm to about 5 ppm, of the MRL in thewash liquor.

[0156] Preferred transition-metals in the instant transition-metalbleach catalyst include manganese, iron and chromium. Preferred MRL'sherein are a special type of ultra-rigid ligand that is cross-bridged.Such a ligand is non-limitingly illustrated below.

[0157] When each R₈ is ethyl, this ligand is named,5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane.

[0158] Transition-metal bleach catalysts of MRLs that are suitable foruse in Applicants' cleaning compositions are non-limitingly illustratedby any of the following:

[0159] Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

[0160] Diaquo-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II) Hexafluorophosphate

[0161]Aquo-hydroxy-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(III) Hexafluorophosphate

[0162] Diaquo-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II) Tetrafluoroborate

[0163] Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(III) Hexafluorophosphate

[0164] Dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)

[0165] Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

[0166]Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecaneManganese(II)

[0167]Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecaneManganese(II)

[0168]Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecaneManganese(II).

[0169] Suitable transition metal MRLs are readily prepared by knownprocedures, such as taught for example in WO 00/332601, and U.S. Pat.No. 6,225,464.

[0170] Processes of Making and Using of Applicants' Cleaning Composition

[0171] The cleaning compositions of the present invention can beformulated into any suitable form and prepared by any process chosen bythe formulator, non-limiting examples of which are described in U.S.Pat. No. 5,879,584 Bianchetti et al., issued Mar. 9, 1999; U.S. Pat. No.5,691,297 Nassano et al., issued Nov. 11, 1997; U.S. Pat. No. 5,574,005Welch et al., issued Nov. 12, 1996; U.S. Pat. No. 5,569,645 Dinniwell etal., issued Oct. 29, 1996; U.S. Pat. No. 5,565,422 Del Greco et al.,issued Oct. 15, 1996; U.S. Pat. No. 5,516,448 Capeci et al., issued May14, 1996; U.S. Pat. No. 5,489,392 Capeci et al., issued Feb. 6, 1996;U.S. Pat. No. 5,486,303 Capeci et al., issued Jan. 23, 1996 all of whichare incorporated herein by reference.

[0172] Method of Use

[0173] The present invention includes a method for cleaning a situsinter alia a surface or fabric. Such method includes the steps ofcontacting an embodiment of Applicants' cleaning composition, in neatform or diluted in a wash liquor, with at least a portion of a surfaceor fabric then rinsing such surface or fabric. Preferably the surface orfabric is subjected to a washing step prior to the aforementionedrinsing step. For purposes of the present invention, washing includesbut is not limited to, scrubbing, and mechanical agitation. As will beappreciated by one skilled in the art, the cleaning compositions of thepresent invention are ideally suited for use in laundry applications.Accordingly, the present invention includes a method for laundering afabric. The method comprises the steps of contacting a fabric to belaundered with a said cleaning laundry solution comprising at least oneembodiment of Applicants cleaning composition, cleaning additive ormixture thereof. The fabric may comprise most any fabric capable ofbeing laundered in normal consumer use conditions. The solutionpreferably has a pH of from about 8 to about 10.5. The compositions arepreferably employed at concentrations of from about 500 ppm to about15,000 ppm in solution. The water temperatures preferably range fromabout 5° C. to about 90° C. The water to fabric ratio is preferably fromabout 1:1 to about 30:1.

EXAMPLES

[0174] The following materials can be obtained from Aldrich, P.O. Box2060, Milwaukee, Wis. 53201, USA: Epichlorohydrin, 2-ethylhexanol,stannic chloride, tetrahydrofuran, potassium tert-butoxide, 48%hydrobromic acid, methylene chloride, sodium bicarbonate, sodiumsulfate, sulfur trioxide-dimethylformamide complex, diethyl ether,toluene, sulfur trioxide-trimethylamine complex, ethyl acetate,1-octanol, 1-decanol, chlorosulfonic acid, 9-decene-1-ol, dioxane,2,2,3,3,4,4,4-heptafluoro-1-butanol,[(6-hydroxyhexyl)oxy]trimethylsilane, and diethylene glycol monohexylether. Synthesis routes for Examples 3 through 11 are depicted inApplicants' specification under the heading “Processes For MakingOrganic Catalyst”

Example 1 Preparation of (2-Ethylhexyloxy)oxiran-2-ylmethane

[0175] 2-ethylhexanol (20 g, 15 mmol) and stannic chloride (0.20 g, 1mmol) are added to a flame dried, 1 L round bottomed flask equipped withan addition funnel charged with epichlorohydrin (15.62 g, 17 mmol). Thereaction is kept under an argon gas atmosphere and warmed to 90° C.using an oil bath. Epichlorohydrin is dripped into the stirring solutionover 1 hr., followed by stirring at 90° C. for 18 hr. The reaction isfitted with a vacuum distillation head and1-chloro-3-(2-ethyl-hexyloxy)-propan-2-ol is distilled at a temperaturerange of from about 80° C. to about 85° C. under 0.2 mm Hg. The1-chloro-3-(2-ethyl-hexyloxy)-propan-2-ol (5.0 g, 22 mmol) is dissolvedin tetrahydrofuran (50 mL) and stirred and maintained at a temperatureof from about 20° C. to about 25° C. under an argon atmosphere.Potassiutn tert-butoxide (2.52 g, 22 mmol) is added to the stirredsolution and the suspension is stirred at from about 20° C. to about 25°C. for 18 h. to produce the glycidal ether.

Example 2 Preparation of 1-Bromo-3-(2-ethyl-hexyloxy)-propan-2-ol

[0176] 2-ethylhexanol (20 g, 15 mmol) and stannic chloride (0.20 g, 1mmol) are added to a flame dried, 1 L round bottomed flask equipped withan addition funnel charged with epichlorohydrin (15.62 g, 17 mmol). Thereaction is kept under an argon gas atmosphere and warmed to 90° C.using an oil bath. Epichlorohydrin is dripped into the stirring solutionover 1 hr. followed by stirring at 90° C. for 18 hr. Then reaction isfitted with a vacuum distillation head and1-chloro-3-(2-ethyl-hexyloxy)-propan-2-ol is distilled under highvacuum. The 1-chloro-3-(2-ethyl-hexyloxy)-propan-2-ol (5.0 g, 22 mmol)is dissolved in tetrahydrofuran (50 mL) and stirred, while maintaining atemperature of from about 20° C. to about 25° C., under an argonatmosphere. Potassium tert-butoxide (2.52 g, 22 mmol) is added to thesuspension and the temperature is maintained at from about 20° C. toabout 25° C., with stirring, for 18 hr. to produce glycidal ether. Next,48% hydrobromic acid (33 mmoles) is added to the reaction mixture thatis maintained at a temperature of from about 20° C. to about 25° C. andstirred for 1 hr. The reaction is evaporated to dryness, the residuedissolved in methylene chloride (50 mL) and the organic solution washedwith a 10% sodium bicarbonate solution (2×100 mL). The organic solutionis dried with sodium sulfate, filtered and evaporated to dryness toafford a clear oil. This material is used without any furtherpurification.

Example 3 Preparation of4-[(2-Ethylhexyloxymethyl]-1,3,2-dioxathiolane-2,2-dione via SynthesisRoute 3 to 4

[0177] Sulfur trioxide-dimethylformamide complex (9.8 gm, 0.06399 mol.)and toluene (100 ml.) are added to a flame dried 3 neck round bottomedflask, equipped with an argon inlet, condenser, and a magnetic stir bar.The reaction is brought to reflux, and once at reflux,2-ethylhexyloxy)oxiran-2-ylmethane (10.0 gm, 0.054 mol.) is added andthe reaction refluxed for 45 minutes. The reaction is cooled to roomtemperature, diluted with diethyl ether (50 ml) and the resultingorganic solution extracted with a saturated sodium bicarbonate solution.The organic phase is separated, dried with sodium sulfate, filtered, andthe organic filtrate evaporated to dryness. The resulting4-[(2-ethylhexyloxymethyl]-1,3,2-dioxathiolane-2,2-dione can be usedwithout further purification.

Example 4 Preparation of Sulfuric AcidMono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(2-ethyl-hexyloxymethyl)-ethyl]Ester, Internal Salt via Synthesis Route 4 to 5

[0178] Crude cyclic sulfate, toluene, and 3,4-dhydroisoquinoline (1equivalent based on starting glycidal epoxide from cyclic sulfatereaction) is added to a 250 mL round bottomed flask. The reaction ismaintained at a temperature of from about 20° C. to about 25° C. andstirred for 48 hours, upon which a solid/gel forms. The resultingsolid/gel is isolated by filtration, to produce the desired productin >50% yield based on starting glycidal epoxide. Optionally, theproduct can be further purified by crystallization from an appropriateorganic solvent.

Example 5 Preparation of Sulfuric AcidMono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(2-ethyl-hexyloxymethyl)-ethyl]Ester, Internal Salt via Synthesis Route 2 to 6 to 5

[0179] 1-Bromo-3-(2-ethyl-hexyloxy)-propan-2-ol, (19.25 gm., 0.072moles), 3,4-Dihydroisoquinoline (9.45 gm., 0.072 moles) and dryacetonitrile (150 mL) is added to a 250 mL round bottomed flask. Thereaction vessel is placed in a 50° C. oil bath and the reaction stirredfor 48 hours under an atmosphere of argon gas. The reaction is thencooled to from about 20° C. to about 25° C., then sulfurtrioxide-trimethylamine complex (10.0 gm., 0.072 moles) is added, andthe reaction is brought to reflux. After stirring at reflux for 1 hour,the reaction is cooled to from about 20° C. to about 25° C. and thenevaporated to dryness at reduced pressure, and the resulting residue issuspended in water (100 mL) at 90° C. for 15 minutes. The resultingsolids are then isolated by filtration, and purified by crystallizationfrom hot ethyl acetate to obtain the product as a white solid.

Example 6 Preparation of Sulfuric AcidMono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(octyloxymethyl)-ethyl] Ester,Internal Salt via Synthesis Route 2 to 8 to 5

[0180] 1-Bromo-3-(octyloxy)-propan-2-ol (1 equiv.), prepared accordingto Example 2 (except 1-octanol is substituted for 2-ethylhexanol), istreated with sulfur trioxide-DMF complex (1 equiv.) in stirringacetonitrile. The reactant mixture is stirred and maintained attemperature of from about 20° C. to about 25° C. for 2 hours followed byaddition of sodium carbonate (3 equiv.). The resulting mixture isstirred and maintained at temperature of from about 20° C. to about 25°C. for 18 hours to obtain the Sulfuric acidmono-(1-bromomethyl-2-octyloxy-ethyl) ester, sodium salt.3,4-dihydroisoquinoline (1 equiv.) is then added to the stirred mixtureand the reaction is stirred at 50° C. for 24-48 hours to obtain theproduct.

Example 7 Preparation of Sulfuric AcidMono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(decyloxymethyl)-ethyl] Ester,Internal Salt via Synthesis Route 3 to 7 to 6 to 5

[0181] 2-Decyloxymethyl-oxirane (1 equiv.), prepared according toExample 1 (except 1-decanol is substituted for 2-ethylhexanol), isdissolved in acetonitrile and warmed to 70° C. Stannic chloride (0.1equiv.) is added to the reaction, which is maintained at 70° C. withstirring for 24-48 hours to give the oxazolidine. The reaction is cooledto from about 20° C. to about 25° C. and chlorosulfonic acid (1 equiv.)is added to the reaction at a temperature of from about 20° C. to about25° C. to yield the product, through sulfation of the putativeintermediate 1-Decyloxy-3-(3,4-dihydro-isoquinolin-2-yl)-propan-2-ol.

Example 8 Preparation of Sulfuric AcidMono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(9-deceneoxymethyl)-ethyl]Ester, Internal Salt via Synthesis Route 3 to 4 to 5

[0182] Glycidal ether (1 equiv.), prepared according to Example 1,(except 9-decene-1-ol is substituted for 2-ethylhexanol) is added dropwise to a stirred suspension of sulfur trioxide dimethylformamidecomplex (1 equiv.) in dioxane over 1 hour at 45° C. to give4-Octyl-[1,3,2]dioxathiolane 2,2-dioxide. The dioxane is removed underreduced pressure and the residue dissolved in acetonitrile. Then3,4-dihydroisoquinoline (1 equiv.) is added to the stirring solution andthe reaction is maintained at temperature of from about 20° C. to about25° C. with stirring for 24-48 hours. As the reaction mixture thickens,additional acetonitrile is added to aid in stirring. The product iscollected as a solid, washed five times with acetone, and allowed to airdry.

Example 9 Preparation of Sulfuric AcidMono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(2,2,3,3,4,4,4-heptafluorobutyloxymethyl)-ethyl]Ester, Internal Salt via Synthesis Route 3 to 4 to 5

[0183] Sulfuric acidmono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(2,2,3,3,4,4,4-heptafluorobutyloxymethyl)-ethyl]ester, internal salt, is prepared according to Example 8, except9-decene-1-ol is replaced with 2,2,3,3,4,4,4-heptafluoro-1 butanol.

Example 10 Preparation of3-{3-[1,1-bis(Methylethyl)-2-methyl-1-silapropoxy]propoxy}-2-(2-3,4-dihydroisouinolylmethyl)propanesulfonicAcid, Internal Salt via Synthesis Route

[0184]3-{3-[1,3-dimethyl-2-(methylethyl)-2-silabutoxy]propoxy}-2-(2-3,4-dihydroisouinoly)propanesulfonicacid, internal salt via synthesis route acid, internal salt, is preparedaccording to Example 8, except 9-decene-1-ol is replaced with3-[1,1-bis(methylethyl)-2-methyl-1-silapropoxy]propane-1-ol (preparedaccording to the method of Lee et al., Tetrahedron Letters, 1996, No.21,pp. 3663-3666).

Example 11 Preparation of Sulfuric AcidMono-{(2-(3,4-dihydro-isoguinolin-2-yl)-1-[2-(2-hexyloxy-ethoxy)-ethoxymethyl]-ethyl}Ester, Internal Salt via Synthesis Route 3 to 4 to 5

[0185] Sulfuric acidmono-{2-(3,4-dihydro-isoquinolin-2-yl)-1-[2-(2-hexyloxy-ethoxy)-ethoxymethyl]-ethyl}ester, internal salt, is prepared according to Example 8, except9-decene-1-ol is replaced with diethylene glycol mono hexylether.

Example 12

[0186] Bleaching detergent compositions having the form of granularlaundry detergents are exemplified by the following formulations. A B CD E F Linear alkylbenzenesulfonate 20 22 20 15 20 20 C₁₂Dimethylhydroxyethyl 0.7 1 1 0.6 0.0 0.7 ammonium chloride AE3S 0.9 0.00.9 0.0 0.0 0.9 AE7 0.0 0.5 0.0 1 3 1 sodium tripolyphosphate 23 30 2317 12 23 Zeolite A 0.0 0.0 0.0 0.0 10 0.0 1.6R Silicate 7 7 7 7 7 7Sodium Carbonate 15 14 15 18 15 15 Polyacrylate MW 4500 1 0.0 1 1 1.5 1Carboxy Methyl Cellulose 1 1 1 1 1 1 Savinase 32.89 mg/g 0.1 0.07 0.10.1 0.1 0.1 Natalase 8.65 mg/g 0.1 0.1 0.1 0.0 0.1 0.1 Brightener 150.06 0.0 0.06 0.18 0.06 0.06 Brightener 49 0.1 0.06 0.1 0.0 0.1 0.1Diethylenetriamine 0.6 0.3 0.6 0.25 0.6 0.6 pentacetic acid MgSO₄ 1 1 10.5 1 1 Sodium Percarbonate 0.0 5.2 0.0 0.0 0.0 0.0 Photobleach 0.00300.0015 0.0015 0.0020 0.0045 0.0010 Sodium Perborate Monohydrate 4.4 0.03.85 2.09 0.78 3.63 NOBS 1.9 1.9 1.66 1.77 0.33 0.75 TAED 0.58 0.58 0.510.0 0.015 0.28 Organic Catalyst* 0.0185 0.0185 0.0162 0.0162 0.01110.0074 Sulfate/Moisture Balance to Balance to Balance to Balance toBalance to Balance to 100% 100% 100% 100% 100% 100%

[0187] Any of the above compositions is used to launder fabrics at aconcentration of 3500 ppm in water, 25° C., and a 25:1 water:clothratio. The typical pH is about 10 but can be can be adjusted by alteringthe proportion of acid to Na- salt form of alkylbenzenesulfonate.

Example 13

[0188] Bleaching detergent compositions having the form of granularlaundry detergents are exemplified by the following formulations. A B CD E Organic Catalyst* 0.14 0.40 0.14 0.20 0.07 Sodium Percarbonate 5.300.00 0.00 4.00 0.00 Sodium Perborate Monohydrate 0.00 5.30 3.60 0.004.30 Linear Alkylbenzenesulfonate 12.00 0.00 12.00 0.00 21.00 C45AE0.6S0.00 15.00 0.00 15.00 0.00 C₂ Dimethylamine N-Oxide 0.00 2.00 0.00 2.000.00 C₁₂ Coco Amidopropyl Betaine 1.50 0.00 1.50 0.00 0.00 Palm N-MethylGlucamide 1.70 2.00 1.70 2.00 0.00 C₁₂ Dimethylhydroxyethylammonium 1.500.00 1.50 0.00 0.00 Chloride AE23-6.5T 2.50 3.50 2.50 3.50 1.00 C25E3S4.00 0.00 4.00 0.00 0.00 Conventional Activator (NOBS) 0.00 0.00 0.600.00 0.00 Conventional Activator (TAED) 2.00 2.80 2.00 1.80 2.30 SodiumTripolyphosphate 25.00 25.00 15.00 15.00 25.00 Zeolite A 0.00 0.00 0.000.00 0.00 Acrylic Acid/Maleic Acid Copolymer 0.00 0.00 0.00 0.00 1.00Polyacrylic Acid, partially neutralized 3.00 3.00 3.00 3.00 0.00 SoilRelease Agent 0.00 0.00 0.50 0.40 0.00 Carboxymethylcellulose 0.40 0.400.40 0.40 0.40 Sodium Carbonate 2.00 2.00 2.00 0.00 8.00 Sodium Silicate3.00 3.00 3.00 3.00 6.00 Sodium Bicarbonate 5.00 5.00 5.00 5.00 5.00Savinase (4T) 1.00 1.00 1.00 1.00 0.60 Termamyl (60T) 0.40 0.40 0.400.40 0.40 Lipolase (100T) 0.12 0.12 0.12 0.12 0.12 Carezyme(5T) 0.150.15 0.15 0.15 0.15 Diethylenetriaminepenta(methylenephos- 1.60 1.601.60 1.60 0.40 phonic Acid) Brightener 0.20 0.20 0.20 0.05 0.20Sulfonated Zinc Phthalocyanine 0.50 0.00 0.25 0.00 0.00 PhotobleachMgSO₄ 2.20 2.20 2.20 2.20 0.64 Na₂SO₄ Balance Balance Balance BalanceBalance to 100% to 100% to 100% to 100% to 100%

[0189] Any of the above compositions is used to launder fabrics at aconcentration of 2500 ppm in water, 25° C., and a 15:1 water:clothratio. The typical pH is about 9.5 but can be can be adjusted byaltering the proportion of acid to Na- salt form ofalkylbenzenesulfonate.

Example 14

[0190] Bleaching detergent compositions having the form of granularlaundry detergents are exemplified by the following formulations. A B CD E Organic Catalyst* 0.06 0.34 0.14 0.14 0.20 Sodium Percarbonate 5.300.00 0.00 0.00 0.00 Sodium Perborate Monohydrate 0.00 9.00 17.60 9.009.00 Linear Alkylbenzenesulfonate 21.00 12.00 0.00 12.00 12.00 C45AE0.6S0.00 0.00 15.00 0.00 0.00 C₂ Dimethylamine N-Oxide 0.00 0.00 2.00 0.000.00 C₁₂ Coco Amidopropyl Betaine 0.00 1.50 0.00 1.50 1.50 Palm N-MethylGlucamide 0.00 1.70 2.00 1.70 1.70 C₁₂ Dimethylhydroxyethylammonium 1.001.50 0.00 1.50 1.50 Chloride AE23-6.5T 0.00 2.50 3.50 2.50 2.50 C25E3S0.00 4.00 0.00 4.00 4.00 Conventional Activator (NOBS) 0.00 0.00 0.001.00 0.00 Conventional Activator (TAED) 1.80 1.00 2.50 3.00 1.00 SodiumTripolyphosphate 25.00 15.00 25.00 15.00 15.00 Zeolite A 0.00 0.00 0.000.00 0.00 Acrylic Acid/Maleic Acid Copolymer 0.00 0.00 0.00 0.00 0.00Polyacrylic Acid, partially neutralized 0.00 3.00 3.00 3.00 3.00 SoilRelease Agent 0.30 0.50 0.00 0.50 0.50 Carboxymethylcellulose 0.00 0.400.40 0.40 0.40 Sodium Carbonate 0.00 2.00 2.00 2.00 2.00 Sodium Silicate6.00 3.00 3.00 3.00 3.00 Sodium Bicarbonate 2.00 5.00 5.00 5.00 5.00Savinase (4T) 0.60 1.00 1.00 1.00 1.00 Termamyl (60T) 0.40 0.40 0.400.40 0.40 Lipolase (100T) 0.12 0.12 0.12 0.12 0.12 Carezyme (5T) 0.150.15 0.15 0.15 0.15 Diethylenetriaminepenta(methylenephos- 0.40 0.001.60 0.00 0.00 phonic Acid) Brightener 0.20 0.30 0.20 0.30 0.30Sulfonated Zinc Phthalocyanine 0.25 0.00 0.00 0.00 0.00 PhotobleachMgSO₄ 0.64 0.00 2.20 0.00 0.00 Na₂SO₄ Balance Balance Balance BalanceBalance to 100% to 100% to 100% to 100% to 100%

[0191] Any of the above compositions is used to launder fabrics at aconcentration of 2500 ppm in water, 25° C., and a 15:1 water:clothratio. The typical pH is about 9.5 but can be can be adjusted byaltering the proportion of acid to Na- salt form ofalkylbenzenesulfonate.

Example 15

[0192] A bleaching detergent powder comprises the following ingredients:Component Weight % Organic Catalyst* 0.07 TAED 2.0 Sodium PerborateTetrahydrate 10 C₁₂ linear alkyl benzene sulfonate 8 Phosphate (assodium tripolyphosphate) 9 Sodium carbonate 20 Talc1 5 Brightener,perfume 0.3 Sodium Chloride 25 Water Balance to 100%

Example 16

[0193] A laundry bar suitable for hand-washing soiled fabrics isprepared by standard extrusion processes and comprises the following:Component Weight % Organic Catalyst* 0.2 TAED 1.7 NOBS 0.2 SodiumPerborate Tetrahydrate 12 C₁₂ linear alkyl benzene sulfonate 30Phosphate (as sodium tripolyphosphate) 10 Sodium carbonate 5 Sodiumpyrophosphate 7 Coconut monoethanolamide 2 Zeolite A (0.1-10 micron) 5Carboxymethylcellulose 0.2 Polyacrylate (m.w. 1400) 0.2 Brightener,perfume 0.2 Protease 0.3 CaSO₄ 1 MgSO₄ 1 Water 4 Filler** Balance to100%

Example 17

[0194] A laundry detergent composition suitable for machine use isprepared by standard methods and comprises the following composition:Weight % Component Formula A Formula B Organic catalyst* 0.82 1.0 TAED7.20 10.0 Sodium Perborate Tetrahydrate 9.2 8.0 Sodium Carbonate 23.7421.0 Anionic surfactant 14.80 12.0 Alumino Silicate 21.30 18.0 Silicate1.85 0.00 Diethylenetriaminepentacetic acid 0.43 0.3 Nonionic surfactant0.00 0.5 Polyacrylic acid 2.72 2.0 Brightener 0.23 0.3 Polyethyleneglycol solids 1.05 0.00 Sulfate 8.21 17.0 Perfume 0.25 0.25 Water 7.726.7 Processing aid Balance Balance to 100% to 100%

[0195] The composition is used to launder fabrics at a concentration insolution of about 1000 ppm at a temperature of 20-40° C. and a water tofabric ratio of about 20:1.

Example 18 Method of Preparing a Starch Encapsulated Particle Comprisingthe Applicants' Organic Catalyst

[0196] 151 g of the Applicants' organic catalyst according to any ofExamples 1-11 above was slowly added to 7,550 g of an aqueous starchsolution (33 wt % solids) in a high-shear mixer for 2 minutes. 190 g ofsodium carbonate (which is dissolved in 498 g water) is added to thismixture, and the resulting mixture is mixed for 5 minutes in ahigh-shear mixer. This mixture is then spray dried using a DrytecCompact spray drier™ with an inlet temperature of 190° C. and an outlettemperature of 90° C., and with the exhaust fully open to form a starchencapsulated particle comprising 4.9 wt % Applicants' organic catalyst,81 wt % starch, 6.2 wt % sodium carbonate and 7.9 wt % water.

[0197] While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. An organic catalyst having the following formula:

wherein: R₁ is a aryl or heteroaryl group that can be substituted orunsubstituted; R₂ is a substituted or unsubstituted alkyl; R₁ and R₂when taken together with the iminium form a ring R₃ is a C₁ to C₂₀substituted alkyl; R₄ is the moiety Q_(t)—A wherein: Q is a branched orunbranched alkylene t=0 or 1 and A is an anionic group selected from thegroup consisting of SO₃O⁻, SO₃ ⁻, CO₂ ⁻, OCO₂ ⁻, OPO₃ ²⁻, OPO₃H⁻ andOPO₂ ⁻; R₅ is the moiety —CR₁₁R₁₂—X—G_(b)—X_(c)—[(CR₉R₁₀)_(y)—O]_(k)—R₈wherein: each X is independently selected from the group consisting ofO, S, N—H, or N—R₈; and each R₈ is independently selected from the groupconsisting of alkyl, aryl and heteroaryl, said R₈ moieties beingsubstituted or unsubstituted, and whether substituted or unsubsitutedsaid R₈ moieties having less than 21 carbons; each G is independentlyselected from the group consisting of CO, SO₂, SO, PO and PO₂; R₉ andR₁₀ are independently selected from the group consisting of H and C₁-C₄alkyl; and R₁₁ and R₁₂ are independently selected from the groupconsisting of H and alkyl, or when taken together may join to form acarbonyl; and b=0 or 1; c can=0 or 1, but c must=0 if b=0; y is aninteger from 1 to 6; k is an integer from 0 to 20; and R₆ is H, or analkyl, aryl or heteroaryl moiety; said moieties being substituted orunsubstituted.
 2. The catalyst of claim 1 wherein: R₁, R₂, and R₆ are asdefined in claim 1; R₃ is a C₁ to C₁₂ substituted alkyl; R₄ is themoiety Q_(t)—A wherein: Q is a C₁ to C₃ alkyl; t=0 or 1 and A is ananionic group selected from the group consisting of OSO₃ ⁻, SO₃ ⁻, CO₂⁻, and OCO₂ ⁻; and R₅ is the moiety —CR₁₁R₁₂—X—G_(b)—X_(c)—R₈ wherein:each X is independently selected from the group consisting of O, S, N—H,or N—R₈; and each R₈ is independently selected from the group consistingof alkyl, aryl and heteroaryl, said R₈ moieties being substituted orunsubstituted, and whether substituted or unsubsituted said R₈ moietieshaving less than 21 carbons; each G is independently selected from thegroup consisting of CO, SO₂, SO, PO and PO₂; R₁₁ and R₁₂ areindependently selected from the group consisting of H and alkyl; b=0 or1; c can=0 or 1, but c must=0 if b=1.
 3. The catalyst of claim 2wherein: R₁ and R₂ when taken together with the iminium form a sixmembered ring; R₃ is a substituted C₂ alkyl; R₄ is OSO₃ ⁻; R₅ is themoiety —CH₂—O—R₈ wherein R₈ is independently selected from the groupconsisting of alkyl, aryl and heteroaryl, said R₈ moiety beingsubstituted or unsubstituted, and whether substituted or unsubsitutedsaid R₈ moiety having less than 21 carbons; and R₆ is the same asdefined in claim
 2. 4. An organic catalyst having the following formula:

wherein: R₁ is a aryl or heteroaryl group that can be substituted orunsubstituted; R₂ is a substituted or unsubstituted alkyl; R₁ and R₂when taken together with the carbon and the nitrogen of theoxaziridinium form a ring; R₃ is a C₁ to C₂₀ substituted alkyl; R₄ isthe moiety Q_(t)—A wherein: Q is a branched or unbranched alkylene t=0or 1 and A is an anionic group selected from the group consisting ofOSO₃ ⁻, SO₃ ⁻, CO₂ ⁻, OCO₂ ⁻, OPO₃ ²⁻, OPO₃H⁻ and OPO₂ ⁻; R₅ is themoiety —CR₁₁R₁₂—X—G_(b)—X_(c)—[(CR₉R₁₀)_(y)—O]_(k)—R₈ wherein: each X isindependently selected from the group consisting of O, S, N—H, or N—R₈;and each R₈ is independently selected from the group consisting ofalkyl, aryl and heteroaryl, said R₈ moieties being substituted orunsubstituted, and whether substituted or unsubsituted said R₈ moietieshaving less than 21 carbons; each G is independently selected from thegroup consisting of CO, SO₂, SO, PO and PO₂; R₉ and R₁₀ areindependently selected from the group consisting of H and C₁-C₄ alkyl;and R₁₁ and R₁₂ are independently selected from the group consisting ofH and alkyl, or when taken together may form a carbonyl; b=0 or 1; ccan=0 or 1, but c must=0 if b=0; y is an integer from 1 to 6; k is aninteger from 0 to 20; and R₆ is H, or an alkyl, aryl or heteroarylmoiety; said moieties being substituted or unsubstituted.
 5. The organiccatalyst of claim 4 wherein: R₁, R₂, and R₆ are as defined in claim 1;R₃ is a C₁ to C₁₂ substituted alkyl; R₄ is the moiety Q_(t)—A wherein: Qis a C₁ to C₃ alkyl; t=0 or 1 and A is an anionic group selected fromthe group consisting of OS₃ ⁻, SO₃ ⁻, CO₂ ⁻, and OCO₂ ⁻; and R₅ is themoiety —CR₁₁R₁₂—X—G_(b)—X_(c)—R₈ wherein: each X is independentlyselected from the group consisting of O, S, N—H, or N—R₈; and each R₈ isindependently selected from the group consisting of alkyl, aryl andheteroaryl, said R₈ moieties being substituted or unsubstituted, andwhether substituted or unsubsituted said R₈ moieties having less than 21carbons; each G is independently selected from the group consisting ofCO, SO₂, SO, PO and PO₂; R₁₁ and R₁₂ are independently selected from thegroup consisting of H and alkyl; b=0 or 1; c can=0 or 1, but c must=0 ifb=1.
 6. The organic catalyst of claim 5 wherein: R₁ and R₂ when takentogether with the carbon and the nitrogen of the oxaziridinium form asix member ring; R₃ is a substituted C₂ alkyl; R₄ is OSO₃ ⁻; R₅ is themoiety —CH₂—O—R₈ wherein R₈ is independently selected from the groupconsisting of alkyl, aryl and heteroaryl, said R₈ moiety beingsubstituted or unsubstituted, and whether substituted or unsubsitutedsaid R₈ moiety having less than 21 carbons; and R₆ is the same asdefined in claim
 5. 7. A cleaning composition comprising the organiccatalyst of claim 1 and an activated peroxygen source.
 8. A cleaningadditive comprising the organic catalyst of claim
 1. 9. A cleaningcomposition comprising the organic catalyst of claim 2 and an activatedperoxygen source.
 10. A cleaning additive comprising the organiccatalyst of claim
 2. 11. A cleaning composition comprising the organiccatalyst of claim 3 and an activated peroxygen source.
 12. A cleaningadditive comprising the organic catalyst of claim
 3. 13. A cleaningcomposition comprising the organic catalyst of claim 4 and an activatedperoxygen source.
 14. A cleaning additive comprising the organiccatalyst of claim
 4. 15. A cleaning composition comprising the organiccatalyst of claim 5 and an activated peroxygen source.
 16. A cleaningadditive comprising the organic catalyst of claim
 5. 17. A cleaningcomposition comprising the organic catalyst of claim 6 and an activatedperoxygen source.
 18. A cleaning additive comprising the organiccatalyst of claim
 6. 19. A process of making an organic catalystcomprising the steps of: a.) providing a substituted or unsubstitutedhalohydrin; b.) reacting said substituted or unsubstituted halohydrinwith a substituted or unsubstituted 3,4-dihydroisoquinoline to form analcohol salt; c.) sulfating said substituted alcohol salt to form anorganic catalyst.
 20. A process of making an organic catalyst accordingto claim 19 wherein the step of providing the halohydrin comprisesreacting a substituted epoxide with a hydrogen halide.
 21. A process ofmaking an organic catalyst comprising the steps of: a.) providing asubstituted epoxide; b.) reacting said substituted epoxide with asubstituted or unsubstituted 3,4-dihydroisoquinoline in the presence ofa Lewis acid catalyst to form a compound comprising an oxazolidinemoiety; c.) reacting said compound comprising an oxazolidine moiety witha Bronsted acid to form an alcohol salt; d.) sulfating said alcohol saltto form an organic catalyst.
 22. A process of making an organic catalystcomprising the steps of: a.) providing a substituted epoxide; b.)reacting said substituted epoxide with SO₃, an SO₃ complex, or mixturesthereof to form a substituted cyclic sulfate; c.) reacting saidsubstituted cyclic sulfate with a substituted or unsubstituted3,4-dihydroisoquinoline to form an organic catalyst.
 23. A process ofmaking a substituted cyclic sulfate comprising the steps of: a.)providing a substituted epoxide; b.) reacting said substituted epoxidewith SO₃, an SO₃ complex, or mixtures thereof to form said substitutedcyclic sulfate.
 24. A process of cleaning a surface or fabric comprisingthe steps of contacting said surface or fabric with a compositioncomprising the organic catalyst of claim 1, then washing or rinsing saidsurface or fabric.
 25. A process of cleaning a surface or fabriccomprising the steps of contacting said surface or fabric with acomposition comprising the organic catalyst of claim 4, then washing orrinsing said surface or fabric.